Ether amine salts of penta-valent organo phosphorus acids



United States Patent 3,238,277 ETHER AMINE SALTS 0F PENTA-VALENT ORGAN 0PHOSPHORUS ACIDS Jack W. Sigan, Minneapolis, Minn., and Tai S. Chao,Homewood, Ill., assignors to Archer-Daniels-Midland Company,Minneapolis, Minn., a corporation of Delaware No Drawing. Continuationof application Ser. No. 860,106, Dec. 17, 1959. This application Aug. 4,1964, Ser. No. 387,494

9 Claims. (Cl. 260-925) This application is a continuation of Serial No.860,- 106, filed December 17, 1959, now abandoned.

This invention relates to ether amine salts of the organo acids of theelements of Group VA, their method of preparation, compositions preparedtherewith and uses. More particularly, this invention preferably relatesto ether amine salts of organo phosphorus acids or aliphatic ether aminesalts of aliphatic acid phosphates, more explicitly definable as alkylether amine salts of alkyl phosphorus acids and especially alkyl etheramine salts of acidic phosphate esters, their method of production anduses particularly as surface active, anti-static and anticorrosionagents, including use as de-icing additives for gasoline and fuels, andin lubricants.

The invention will be better illustrated by demonstrating andillustrating the new and novel organo ether amine phosphorus compoundsas the preferred embodiment of this disclosure and represented by thegeneral formula, as follows:

where R is a substituted or unsubstituted normal or branch chain alkyl,aryl, alkaryl, cycloalkyl, or heterocycloalkyl group, such as methyl,ethyl, n-butyl, isoamyl, cyclohexyl, isoheptyl, isooctyl, isononyl,lauryl, tetrahydrofurfuryl, phenyl, =octylphenyl including halogenatedalkyl, aryl, alkaryl compounds of the character of chlorophenyl,chloromethyl, and the like; a substituted and unsubstituted normal orbranch chain alkoxy, aryloxy, cycloalkoxy, or heterocycloalkoxy groupsuch as methoxy, n-butoxy, isoamoxy, n-hexoxy, isoheptoxy, isooctoxy,tetrahydrofurfuroxy, phenoxy, octylphenoxy, chlorophenoxy, isodecoxy,and the like in which the total number of carbon atoms do not exceed 26and is preferably 1 to 18;

R is the same or a ditferent group selected :from R above or O;

R is alkyl, aryl, cycloalkyl groups of 1-22 carbon atoms such as methyl,ethyl, isopropyl, n-butyl, n-hexyl, cyclohexyl, 2-ethylhexyl, octyl,stearyl, behenyl, etc.;

R and R are the same or different divalent alkylene groups of l-6 carbonatoms such as methylene, ethylene, propylene, butylene, isopropylene,etc.;

2 is a small whole number, including 1 to 3;

b is equal to 4-2;

0 is a small whole number, including 1 or 2;

x is a whole number, including 0 to 20, and

y is a whole number, including 1 to 5.

In general, it may be stated that the ether amine com- 3,238,277Patented Mar. 1, 1966 ponent may be an aliphatic, aromatic, substitutedaliphatic or substituted aromatic ether amine containing 1 to 25 or moreether oxygen atoms in the molecule. Such compounds can be represented bythe general formula:

where R R R z, b, x and y are as described above.

An illustrative example of a preferred ether amine is3-(2-ethylhexoxy)-n-propylamine, which will hereinafter be referred toas Z-ethylhexyl ether amine; its structure can be represented asfollows:

Other suitable lbut non-limiting ether amines includeisopropoxy-n-propylamine, n-butoxy-n-propylamine, iso-=butoxy-n-propylamine, amyloxy-n-propylamine, n-hexoxyn-propylamine,isooctoxy-n-propylamine, ethoxy-ethoxyn-propylamine,butoxy-ethoxyethoxy-n-propyl amine, ethoxyethoxy-ethoxy-n propylamine,phenoxy n propylamine, octylphenoxy-n-propylamine,cyclohexoxy-n-propylamine, tetrahydrofurfuroxy n propylyamine, the etheramines derived from 1-20 ethylene oxide adducts of Gi -C alcohols, andthe like. Other ether amines are those of the character provided in thepatent of R. J. Stenberg, US. 2,983,738, providing amine derivatives ofpropionitrile products having the general structure:

R JO(R O)nCH2CH2CHzNH2 where R is R above, R is R or R and n may be from1 to 30.

In general, many of the ether amines can be conveniently preparedthrough the known methods of cyanoethylation of alcohols, ether alcohols(such as Cellosolves and Carbitols), phenols, ether phenols, and thelike, followed by hydrogenation of the resulting ether nitriles. Thereactions involved can be illustrated by the following:

Tertiary ether amines (those in which z is 3 and b is 1) can be preparedfrom primary and secondary ether amines by known methods of alkylation.For example:

(VII) a or from ether alcohols by reductive alkylation, as follows:

(VIII) /X R1 on whe re R is the same as previously defined,

R is a group from these represented by R or OH,

X is an element of Group VA of the Periodic Table, i.e.,

phosphorus, arsenic, antimony and bismuth and preferably phosphorus.

The above is intended to include the acid esters of orthophosphoricacid, phosphorus acid, phosphonic acid, and phosphinic acid, many ofwhich are commercially available or can be produced by methods known tothe art. A referred class of acidic organophosphorus compounds are theacid esters of ortho-phosphoric acid. This particularly includes themixture of monoand di-substituted phosphates obtained from the reactionof phosphorus pentoxide and an alcohol, such as isobutyl, mixed amyl,n-hexyl, isooctyl, n-octyl, mixed n-octyl-n-decyl, x0 decyl, lauryl,tridecyl and similar alcohols. The method of preparation of suchhosphates is known to the art. The use of the mixture of monoand dialkylphosphates instead of mere dialkyl phosphates, prepared by methods knownto the art, has many advantages. Besides being more readily prepared andavailable at a lower cost, the mixed mono-di-alkyl phosphates havehigher acid value than dialkyl phosphates, and consequently allowincorporation of more ether amine into the molecule whenever desired.They also give salts of lower pour point than similar derivatives ofdialkyl phosphates, and provide other desirable physical properties inconjunction with economical production and commercial usage.

Accordingly, it will be recognized that it is an object of thisinvention to provide the art with ether amine salts of organophosphoruscompounds and substitute other organo acid salts of arsenic, antimonyand bismuth of recognizable chemical equivalence in reaction, as hereindescribed and the method of preparing the same.

A further object of this disclosure is to provide the art with preparedreactants and a method for their preparation including in addition themethod for producing ether amine salts of organophosphorus acidstherefrom.

Another object of this disclosure is to provide the art with novel etheramine salts of an organic phosphate as antistatic and rust inhibitingagents providing economic advantages and serving as improved lubricantand fuel additives in addition to being useful in the formulation ofother compositions and products.

To the accomplishment of the foregoing and related ends, this inventionand improvement in the art then comprises the features herein describedand more particularly illustrated by typical examples, recognizable tothose skilled in the art. The following description sets forth in detailcertain illustrative and exemplary embodiments of the invention, thesebeing indicative, however, of but a few of the varous ways in which thecompounds of this invention and improvement in the art may be made andemployed.

Illustrative but non-limiting examples to exemplify the preparation ofalkyl derivatives of phosphonic acids, as reactants for producing theether amine salts of this invention, are shown, as follows:

4 EXAMPLE I A 5 liter, 3-necked flask was equipped with a stainlesssteel stirrer, a thermometer, a nitrogen inlet, and an 18 inch glasshelices-packed column. The latter was fitted with a variable take-offcolumn head and a reflux condenser. A mixture of 1,767 gms. laurylbromide and 1,219 gms. triethyl phosphite was placed in the fiask andheated to C., with stirring. At this temperature ethyl bromide startedto distill over. The distillation of ethyl bromide continued for aperiod of 11 hours during which the pot temperature rose gradually to235 C. Towards the end of the reaction period nitrogen gas was bubbledthrough the reaction mixture to facilitate the removal of ethyl bromide.A total of 743 gms. ethyl bromide was obtained. The residue wasdistilled under vacuum to remove 215 grams of excess triethyl phosphiteand its isomerization product, namely, di-ethyl ethanephosphonate. Therewas obtained 1,974 gms. (92.4% yield) of crude undistilled di-ethyllauryl phosphonate. Theoretical phosphorus 9.62%; determined, 9.20%.This and similar phosphonates can be purified by vacuum distillation, ifdesired. However, the crude products are satisfactory for use asillustrated by the following example.

EXAMPLE II To prepare a mono-ethyl lauryl acid phosphonate, the di-ethylphosphonate ester, dwcribed in Example I, was saponified with a 0.8 Nsolution of potassium hydroxide in diethylene glycol. 960 gms. of thediethyl ester was heated at l42-16 2 C. for =15 hours with .2500 ml. ofthe KOH solution. The reaction mixture was then acidified with dilute HSO and the acid ester was taken up in methyl iso-butyl ketone. Afterrepeated washing I with salt water and water, the solution was placedunder vacuum and the solvent removed. The residue was a light-browncolored liquid weighing 758 gms. The yield was 86.6%. Analysis showed8.8% phosphorus and acid value 148. This crude product was utilizedsatisfactorily for preparation of the ether amine salts of thisdisclosure. Likewise, comparable analogous aliphatic phosphonates may beprepared as reactants for forming the ether amine salts, as indicated.

EXAMPLE III To prepare a dibasic lauryl phosphonic acid, the diethylester from Example I (800 gms.) was refluxed with 2,050 ml. ofconcentrated HCl for 15 hours. The hot reaction mixture was transferredto a separatory funnel from which the lower aqueous layer was removed.The upper layer was diluted with ether, washed with water, dried, andthe solvent was removed under vacuum. There was obtained 593 gms. (90.1%yield) of a white, wax-like solid which showed the following analysis:phosphorus 9.31% and acid value 343. This solid was used to form anether amine salt as herein described.

The following examples are illustrative of using the above typereactants and the new and useful compounds provided therewith by thisdisclosure. Essentially, the novel ether amine salts of an organicphosphate can be prepared.

The novel ether amine salts of an organic phosphorus acid can beprepared by neutralization of the respective phosphorus acid withapproximately stoichiomet-ric proportions of an ether amine of the classdescribed herein. In mos-t instances, it is advantageous that the pH ofthe reaction mixture be adjusted to substantially neutral, i.e., betweenabout 5.5 and about 7.5, by controlling the amount of ether amineintroduced into the reaction. In the case of ether amines that are veryweak bases, however, a lower pH, for example of the order of 3.0 or 3.5is satisfactory.

EXAMPLE IV 350 grams of mixed monoand dialkyl phosphates, prepared froma commercial grade mixture of C to and ineluding C fatty alcohols, wasplaced in a 1 liter, 3 necked flasked equipped with a stainless steelstirrer, a reflux condenser and a nitrogen gas inlet. With constantstirring and cooling with a water bath, 280 grams of an ether amine(Z-ethyl-hexoxypropyl amine) was added from a dropping funnel during thecourse of 15 minutes. A maximum temperature of 61 C. was observed. Theproduct was a viscous liquid soluble in kerosene and gasoline in allproportions. It showed a pH of 7.2 and a light yellow color. It analyzed5.62% phosphorus and 3.20% nitrogen.

EXAMPLE V 350 grams of isoctyl phosphate prepared by a known method froma commercially available grade of isooctyl alcohol was neutralized andreacted in the manner of Example IV with 342 grams of crudeZ-ethylhexoxy-npropyl ether amine. The product was a light orangecolored liquid having a pH of 7.2. It showed the following analysis:6.14% phosphorus and 3.52% nitrogen. A similar run with a distilledsample of the same ether amine gave a colorless product having an.equivalent analysis. This product is an ether amine salt of isoctylphosphate, named 3-(2-ethylhexoxy) n propylamine isooctyl phosphate; thepreparation is essentially a mixwas suflicient to bring the pH of thesalt in the range of 6.9-7.1, for the condition of reaction.

W 0.7WP (A.V.) M

where In the present example W is 40, A.V. is 225 and, hence, W is equalto 0.112 M. Since the actual amount of ether amine required depends bothon the quality of the amine and the exact shape of the neutralizationcurve of individual compound, slightly less than this amount, namely0.10 M of the individual ether amine, was used at first. The phosphateand the amine were warmed and stirred until a homogeneous product wasobtained. The pH of this product was measured and then additionalamounts of ether amine were added until a pH of 6.9-7.1 was attained.

Table 1 PREPARATION OF ETHER AMINE SALTS OF ISOOO'IYL PHOSPHATES Weightof amines Ether Amine Used Formula M W,., Grams pH Start Total Name:

Isopropyl-ether amine i-CaH7OC3HsNH: 117 11.7 11.9 6. 9 n-Butyl etheramine. 131 13.1 13.7 6. 9 Isobutyl ether amine 131 13. 1 13. 7 6. 9Mixed amyl ether amine. 145 14. 5 16. 7. 0 n-Hexyl ether amine 159 15. 918. 3 6. 9 Isooctyl ether amine 187 18. 7 19. 6 6. 9 0x0 decyl etheramine. 215 21.5 22. 8 7. 0 Tridecyl ether amine 257 25. 7 26. 1 6. 9Butyl Cellosolve ether am 175 17. 18. 7 7.0 Butyl Carbitol ether amine219 21. 9 24. 1 7.0

These salts were pale yellow clear liquids and soluble in gasoline,kerosene, mineral oil and other hydrocarbon solvents.

ture of the ether amine salts of monoand dialkyl phosphates.

EXAMPLE VI An illustration of the preparation of an alkyl ether aminesalt of an acidic organophosphorus compound prepared by other than thephosphate above provided by neutralizing 10 grams of crude mono-ethyllauryl acid phosphonate (Example II) with 5.5 grams of ether amine(2-ethylhexoxypropyl amine) in a 150 ml. beaker. The salt obtained was alight yellow clear liquid, soluble in gasoline, kerosene and lubricantsand under the severe conditions of test, was found to be an excellentcorrosion inhibitor (see Example XIV).

EXAMPLE VII While the above examples show how in ether amine, such asZ-ethylhexoxy propyl amine, was used in this invention, other etheramines can be used to form the solvent soluble corrosion inhibitingsalts embodied herein. For example, Table 1 shows a series of etheramine salts of isooctyl phosphate which were prepared and the essentialconditions of preparation. In each of these 40 g. of a 70% solution ofisooctyl phosphate in mineral spirits was placed in a ta'red containerand a calculated amount of ether amine was added. The calculation wasbased on the following equation and our previous finding that roughly70% of the amine equivalent to the second acid value (thymolphthaleinend point) of the phosphate In addition to preparing many of these etheramine salts in solvent solutions, suitable ether amines and alkylphosphates can be reacted in the absence of solvent, as variouslyindicated herein and shown in the following example:

EXAMPLE VIII The lauryl ether amine (n-C H OC H NH salt of isooctylphosphate was prepared in the absence of a solvent. This ether aminesalt is similarly soluble in gasoline, kerosene, mineral oil and othersolvents and effective as a corrosion inhibitor. Heating to 116 C. wasrequired to obtain a clear homogeneous reaction mixture, but theneutralized salt was a clear liquid at room temperature. The addition ofabout 22.4 grams of the ether amine was required for substantiallyneutralizing and reacting with 20 grams of isooctyl phosphates to a pHof between about 5.5 and 7.5.

EXAMPLE IX As indicated, the preparation of ether amine salts can beconducted with or without the use of a solevnt, in a recognized manner.However, it is sometimes preferable and more convenient to use asuitable solvent, such as kerosene, another suitable hydrocarbonsolvent, or a suitable alcohol solvent. The use of a suitable solventwill facilitate stirring and cooling of the reaction mixture and thesubsequent handling and application of the product. In the event thatthe product is used as a gasoline additive, the product can be preparedand used directly as a concentrated kerosene or other suitable solventsolution. For lubricant application, mineral oil is the preferredsolvent for conducting the reaction. Some additional examples willillustrate the preparation of the ether amine phosphate salts withselective solvents for particular end uses, as follows:

EXAMPLE X Four hundred grams of a 68% by weight solution of isooctylphosphates in mineral spirits was placed in a 1 liter, 3-necked flaskequipped with a stirrer, a reflux condenser and a dropping funnel. Withstirring and passage of nitrogen, 251 g. of an ether amine (Z-ethylhexylpropyl amine) was added during the course of 22 minutes. The productshowed a pH of 7.4. Fifty grams of the phosphate solution was then addedto bring the pH to 7.0. The product was a light yellow clear liquid,giving the following analysis: 5.33% phosphorous and 2.53% nitrogen. Theether amine salt can be used directly, without removing the solvent, asan oil, fuel or gasoline additive, inasmuch as the presence of the smallamount of mineral spirits will not materially affect the performance ofthe oil, gasoline or fuel.

EXAMPLE XI 23 grams of lauryl phosphonic acid in solution in 8 grams ofkerosene was neutralized in a 100 ml. beaker with 16.4 grams of2-ethylhexoxy-n-propylamine. The product was a light yellow liquid of pH7.05. It was diluted with more kerosene to form an 80% by weightsolution and used as a corrosion inhibiting additive for gasoline.

In preparing the phosphate salts, under the conditions of reactionindicated, the ether amines are interchangeable and substituted in thedescribed reactions to obtain desired final physical properties e.g.,the shorter chains for water solubility and the longer chains for oilsolu bility. These ether amine salts e.g. are derived in a similarmanner utilizing e.g. butyl ether amine or lauryl ether amine and thelike and with organophosphorus acids other than acid phosphates i.e.acid phosphonates and phosphinates, by a process as described. Examplesillustrative of our novel ether amine salts of alkyl acid phosphateshaving beneficial corrosion-inhibiting properties are hereinafterprovided.

As shown in the above examples, crude as well as purified ether aminescan be used in the preparation of organophosphorus salts of thisinvention and utilized in the manner shown in the test examples forpractical application. The color and clarity of the product dependsnaturally on the quality of the amine as well as of the phosphate used.However, it is a discovery of this invention that light colored aminesalts can often be prepared from dark colored phosphates, provided thata purified ether amine is used. It appears that the colorcausingimpurities in the acidic phosphates became lighter colored uponneutralization in the reaction.

In commercial production where crude ether amine is used, the color ofthe salt product can often be improved if necessary by decolorizationwith a suitable decolorization agent such as Filtrol, Darco or Nuchar,as shown in the following example.

8. EXAMPLE XII About 50 grams of the orange-colored Z-ethylhexyl etheramine salt of isooctyl phosphates was heated for 30 minutes on a steambath with 5 g. of an activated carbon bleaching agent, 10 g. of acommercial filter aid and 150 ml. of hexane. The mixture was suctionfiltered through a *Biichner funnel and the filtrate was evaporatedunder vacuum. A light yellow colored viscous liquid was obtained whenall the solvent was removed. Otherwise, the solvent solutions of theprepared salts may be filtered through suitable commercially availablesolid adsorbents such as Filtrol, Hyflo Super-Cel, silica gel, etc.

The following are illustrative of test samples and manner of use inpractical applications of the preferred ether amine salts.

EXAMPLE XIII 0.3570 gram of the 2-ethyl hexyl either amine salt ofisooctyl phosphate (Example V) was stirred into 250 milliliters of acommercial gasoline containing no corrosion inhibitor. The mixture wasstirred until a clear solution was obtained. Three milliliters of thissolution was then diluted to 500 millilters with the same gasoline. Thisrepresents a gasoline containing 0.00856 gram per liter of the aminesalt and is equivalent to the presence of 3 lbs. of this activeingredient in 1000 barrels of gasoline. Corrosion tests according toASTM method D665-54 showed the absence of any rust after 20 hrs. at 100F. in synthetic seat water. Control samples under the same conditions oftest were heavily rusted. The same effectiveness was observed with thebis(2-ethylhexoxy propyl) amine salt of isooctyl phosphate preparedEXAMPLE XIV Percent rust in synthetic sea water Concentration, lbs/1,000bbl.

Ether amine used in the preparation of salt exemplified by isooctylphosphate i-Propyl ether amine n-Butyl ether amine i-Butyl ether amine.Mixed amyl ether amine n-Hexyl ether amine. LOctyl ether amine...

0x0 deeyl ether amine" Trldecyl ether amine Butyl Cellosolve etheramine. Butyl Carbitol ether amine H QQQQOOOQOO ooaoowceooocam Testmethod ASTM method D665-54, modified according to military specifieatlonMIL-25017 (ASG) and its amendment-1.

EXAMPLE XV This example illustrates that ether amine salts oforganophosphorus acids other than the exemplary alkyl phosphates arealso effective corrosion inhibitors for oils, gasolines and fuels. Asample of the Z-ethylhexyl ether amine salt of monoethyl laurylphosphonate (Example VI) was diluted with one fourth of its Weight ofkerosene to give an solution. 0.3570 gram of the kerosene solution wasdissolved in 250 ml. of depolarized isooctane to provide a stocksolution. Three milliliters of the stock solution was diluted with theisooctane to 500 ml. to prepare a test solution. 300 ml. of this testtest solution was used in the ASTM D665-54 test for corrosioninhibitors, using 30 ml. synthetic sea water. The concentration of theactive ingredient was thus 0.00685 gram per liter, equivalent to 2.4lbs. per 1000 bbl. of isooctane. After 20 hours at 2 F., the testspecimen 9 showed the complete absence of rust and corrosion. Thecontrol sample was badly rusted EXAMPLE XVI This example illustrates theefiectiveness of the ether amine salts of this invention as corrosioninhibitor in mineral oil compositions. 0.1428 gram of the 2-ethylhexylether amine salt of isooctyl phosphate was dissolved in 100 millilitersof light white mineral oil. Five milliliters of this solution wasdiluted to 500 ml. with the same mineral oil. Two hundred fiftymilliliters of this diluted solution was used in the ASTM D665-54 testfor rust inhibition. After 20 hrs. at 140 i2 F. in the presence of 25ml. of distilled water, the test specimen showed the complete absence ofrust or corrosion.

The prepared illustrated compounds were soluble and compatible withgasoline, kerosene, suitable alcohols and hydrocarbon solvents, fueloils, lubricating oils and greases and may be mixed therewith in desiredproportions for beneficial advantage without detriment to the mixture.As indicated above these ether amine salts are effective at a level ofabout 1.6 to 3 pounds in 1000 bbl. of gasoline. Relatively larger andsmaller proportions of the herein described ether amine salts of organicacid phosphorus compounds can be mixed with gasoline, fuels andlubricants with beneficial results. In lubricants about 0.01% to 20% ofthe ether amine salts may be used and in gasoline about 0.5 to 20 poundsper 1000 bbl. may be used. In addition to their being additative tolubricants, including mineral oils, synthetic lubricants, lubricatinggreases, cutting oils, and metal working lubricants, the said salts maybe utilized in solutions or dispersions as lubricants, surfactants,d-ispersants, 'anti-oxidants, an additive to drilling muds, oil flowlines and the like, and as anti-water and extreme pressure additives. Ingeneral the products herein described when added in small amounts ofabout 0.11 to to oils and oil well sealing fluids aid in earthpenetration and absorbency for oil storage.

Another valuable property of the ether amine salts of this invention istheir ability to dissipate static electricity from surfaces ofhydrophobic materials. This includes hydrophobic textile fibers such asnylon, Acrilon, Orlon, etc., and other shaped articles made ofhydrophobic polymers. The following example demonstrates itseffectiveness as an antistatic agent for vinyl floor tile.

EMMPLE XVII A cigarette ash test was set up according to the methoddescribed by U.S. Patent No. 2,778,748 with a few modifications. A 3 x8" piece of glass plate was placed horizontally over two /2 pint glassjars. A thin layer of fresh cigarette ash was spread on the glass and ascale was placed behind the glass plate for measuring the verticaldistance above the, glass surface. A 1 /2" x 3" strip cut from a vinylfloor tile was placed on several layers of paper and rubbed vigorouslyfor about 20 strokes with a clean paper towel. The tile strip wasimmediately placed over the cigarette ash with the rubbed surface facingthe ash. The tile strip was gradually lowered until the ash began to beattracted by the tile and the distance between the tile and the glasssurface was measured. With untreated vinyl tile the distance was 23 cm.,depending upon relative humidity of the room.

Identical tile strips were then treated with the ether amine salts ofthis invention. The simplest method was to place a few drops of amineral spirits solution containing 80% of the salts of Example VII onthe tile, spread it evenly over the tile surface with a paper towel andwipe off the excess. After drying at room temperature for about an hourthe strip was tested in the same manner as done with the untreated tile.The tile can now be lowered into direct contact with the ashes withoutattracting them. This has been done for a number of ether i0 aminesshown in Table 1 and complete de-statification was observed for those inwhich R is isopropyl, isobutyl, butyl Cellosolve and butyl Carbitol,while the others showed lower but significant efifects.

Although mineral spirits were used in the above example, other solvents,vehicles and pigmented and varnish vehicles can be used as well.Suitable solvents include aliphatic, cycloaliphatic and aromatichydrocarbons, alcohols, aqueous emulsions, halogenated hydrocarbons,ketones and esters. The solution can be applied by wiping, brushing,spraying, dipping or other suitable means of applying antistatic agentsto the surface of materials which are known to the art. Theconcentration of the solutions can vary from 0.5 to 50% by weight.

The ether amine salts of this invention are also useful as solubilizingagents for metal salts in mineral oil. For example, a zinc salt of a P 8addition product to an unsaturated fatty material or olefin which isinsoluble in mineral oil can be solubilized with the addition of a minoramount, such as 25% by weight of the zinc salt, of the 2-ethylhexylether amine salt of isooctyl phosphate.

A selective group of the ether amine salts of alkyl acid phosphates,having 412 carbon atoms in the alkyl chains are also useful as de-icingor anti-stalling additives to gasolines and fuels. In such anapplication the alkyl amine salts described show unexpected and superiordeicing or anti-stalling efficiency over other known availablecommercial materials. These salts also exhibit advantageous pour point,water tolerance solubility and stability characteristics. They are alsoeconomically favorable on a cost basis.

The effectiveness of the ether amine salts of alkyl acid phosphates inmineral oil systems shows the use of these compounds as corrosioninhibitors in mineral lubricating oils, industrial lubricants, hydraulicfluids, cutting oils, metal working lubricants, in oil-water emulsionsystems such as soluble oils, fire-retardant hydraulic fluids, and inautomobile cooling systems in which a small amount of mineral oilcomposition is often used in combat corrosion. The addition of a smallportion of the ether amine salts, e.g., 0.001% to 10% aids in preventingcorrosion. In concentrated solution in petroleum solvents the pourpoints are from 10 to about 20 F. lower than known commercial products.

Many of the ether amine salts specified in this disclosure are alsocompatible with polymers and resins. For example, the 2-ethylhexyl etheramine salt of isooctyl phosphate was found to be soluble in an alkydresin at a level of 20% by weight. Also being in mineral spirits andother paint and lacquer solvents the use as corrosion inhibitor in paintsystems, such as in alkyd house paints, water-thinned paints, lacquers,enamels, in printing inks and similar systems.

The ether amine salts of this invention are also useful as surfactantswhich include liquid detergents, degreasing agents in solvents, drycleaning detergents, emulsifying agents and wetting agents, as textilelubricants, softeners and conditioning agents, and as herbicidal,fungicidal and insecticidal agents.

Being soluble in mineral spirits and certain other hydrocarbon paint andlacquer solvents, the ether amine salts are also useful in resinouspaint, lacquer and enamel vehicles at levels of from about 01-10%, ascorrosion inhibiting agents.

It is apparent that many modifications and variations of this inventionas hereinbefore set forth may be made without departing from the spiritand scope thereof. The specific embodiments described are given by wayof example only and invention is limited only by the terms of theappended claims.

What is claimed is:

1. Alkyl ether amine salts of (l) a mixture of at least onemonoalkyl-substituted ortho-phosphoric acid and at least onedialkyl-substituted ortho-phosphoric acid wherein each alkyl substituentgroup of said ortho-phosphoric acids contains 1-26 carbon atoms, saidortho-phosphoric acids being otherwise unsubstituted, and (2) an alkylether amine having the formula:

wherein R is an alkyl group of 122 carbon atoms, each of R and R is adivalent alkylene group of 16 carbon atoms, x is an integer from 0-20, yis an integer from 15, and z is an integer from 1-3.

2. Alkyl ether amine salts of claim 1 wherein each alkyl substituentgroup of said ortho-phosphoric acids is isooctyl.

3. Alkyl ether amine salt of claim 1 wherein at least one of said alkylsubstituent groups is isooctyl.

4. Alkyl ether amine salt of claim 1 wherein x is zero, y is one, and zis one.

5. 3-(2-ethylhexoxy)-n-propyl amine salt of a mixture of isooctylortho-phosphoric acid and diisooctyl orthophosphoric acid.

6. 3-(isopropoxy)-n-propylamine salt of a mixture of isooctylortho-phosphoric acid and diisooctyl orthophosphoric acid.

7. 3-(n-butoxy)-n-propylamine salt of a mixture of isooctylortho-phosphoric acid and diisooctylortho References Cited by theExaminer UNITED STATES PATENTS OTHER REFERENCES Adler et al.: ChemicalIndustries, October 1942, pp. 5 l 6, 5 l 8.

CHARLES B. PARKER, Primary Examiner.

FRANK M. SIKORA, DELBERT R. PHILLIPS,

Assistant Examiners.

5/1950 Smith et al. 260455 x

1. ALKYL ETHER AMINE SALTS OF (1) A MIXTURE OF AT LEAST ONEMONOALKYL-SUBSTITUTED ORTHO-PHOSPHORIC ACID AND AT LEAST ONEDIALKYL-SUBSTITUTED ORTHO-PHOSPHORIC ACID WHEREIN EACH ALKYL SUBSTITUENTGROUP OF SAID ORTHO-PHOSPHORIC ACIDS CONTAINS 1-26 CARBON ATOMS, SAIDORTHO-PHOSPHORIC ACIDS CONTAINS 1-26 CARBON ATOMS, SAID ORTHO-PHOSPHORICACIDS BEING OTHERWISE UNSUBSTITUTED, AND (2) AN ALKYL ETHER AMINE HAVINGTHE FORMULA: